Chemical reactor and recovery unit



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ip e Q-um 3W June 19, 1951 A. DIGREEN CHEMICAL REACTOR" AND RECOVERY UNIT Original Fileg March 25, 1945 5 Sheets-Sheet 2 E771 YL ENE VA Po/as 5 MERCURY 1 11/ I27 1:: l PRAY v l I i A v v v i 709 .724 lfi'encroz fr WA r22 5541. N 4110010 ITHYLENE P 1 MER REMOVED By HA /vz I78 r DEA/N f ikfiis/w WATER [NLET FfC-Z June 19, 1951 A. D. GREEN I CHEMICAL REACTOR AND RECOVERY UNIT 5 Sheets-Sheet 3 Original Filed March 25,-1943 Fibs Gases 1'0 Jiea ecfor Sol/d Polymer 76 Dr/er Pcd'e red Vapars Recycle Gas (ompr es'sor'zs a w .2.. 4 m ge Q ll u 8 1 WW d 0A June 19, 1951 A. D. GREEN 2,557,910 CHEMICAL REACTOR AND RECOVERY UNIT Original Filed March 25, 1943 5 Sheets-Sheet 4 Flash Gases 76 Recycle Gas Compressors Fias fi Dram Dry Recycle Gas 3 342 Dram I/fbrafinq Re ac for June19, 1951 An-GEE,- 2,557,910

' CHEMICAL REACTOR AND ECOVERY UNIT Original Filed Marcih 25, 1943 5 Sheets-Sheet 5 f'l a slz Gases 76 lPecycle Gas Compfless ons- Flash 1 Tank - Flask Gases from f l eac {107; 4/7 Pp r Drum lurry 4 'm'ergency LmTo' sfl'lpping Drum mm /r2/et Patented June 19, 1951 '1 255mm I ENI'EFEE STATES PATENT OFFECE CHEMICAL REACTUR AND RECOVERY UNIT Arthur Donald Green, Craniord, N. J., assignor to Standard Oil Development Company, a corporation of Delaware Original application November 25, 1943, Serial Divided and this application June 30, 1948, Serial No. 36,074

This invention relates to polymerization procthat several serious problems are presented by esses and apparatus and particularly to processes the process. In the first place, it is necessary to and apparatus for the low temperature polyshut or seal ofi the reaction space from the atmerization of isoolefins or mixtures of isoolefins mosphere in order to prevent escape of inflamand diolefins. mable materials therefrom which would create It has been known for some time that high a substantial fire and explosion hazard. In the molecular weight polymers, i. e., having a nioleosecond place, the polymer must be brought from ular weight of from about l5,000 25,000 up to a temperature of around 40 C. or lower up to 300,000 or more (as determined by the Staudinger room temperature or above, a range over which method) are obtained if isoolefins, such as isothe polymer becomes very tacky and tends to agbutylene, are contacted with Friedel-Crafts type glomerate. Finally, it is necessary to bring the catalysts such as aluminum chloride and the polymer from a reaction zone in which it is aslike at temperatures below about l0 C. (See, sociated with highly volatile, inflammable mafor example, Mueller-Cunradi U. S. Patent No. terials out into the atmosphere sufficiently free 2,203,873, issued June 11, 1940.) More recently it from inflammable materials that no fire or exwas found that a copolymer which is curable with plosion hazard is presented. sulfur is obtained if a mixture of about 70 to 99.5 In the original laboratory work, the reaction weight percent of an isoolefin such as isobutylene Was carried out batchwise and the polymer Was with about 30 to 0.5 weight percent of a coniuremoved as a large lump or mass. It became gated diolefin such as butadiene or isoprene is apparent at once that the handling of such treated with a solution of a Friedel-Crafts type lumps or masses of polymer would involve a numcatalyst such as aluminum chloride in a noncornber of serious disadvantages when this reaction plex forming low freezing solvent such as methyl was attempted on a larger scale. For example, or ethyl chloride and at temperatures of between in order adequately to wash out the residual cat- 10 C. and 160 0., preferably between l0 alyst and to remove completely the traces of vola- C. and l03 C. (See, for example, Australian tile materials, it was necessary to wash and steam Patent No. 112,875, issued July 31, 1941.) These he p ym riza s in he vy ma t c ins app polymerizations have been conducted in'the presratus such as kneaders, mills or Banbury mixers. once of an internal refrigerant such as liquefied This m xin or n a n in a n ry yp m ethylene, in which case the heat of reaction is has been considered essential in the manufacture removed directly by evaporation of part of the f l w mp u i l fi io fin 0p yethylene Without the necessity for transferring me at S e these D Y are ulcan heat through the surfaces of the reaction vessels ab and t W fO t a those p ym s Wh ch or through cooling coils arranged in the reaction were not so mixed or kneaded y eld d vulcanizvessels. On the other hand, there are certain ates containing blisters and flaws which rendered definite advantages to be gained by conducting 40 e vu a a practically useless- Aside f the reaction in the presence of other diluents t it was u d th O a a e Scale the e which have a higher boiling point than ethylene u d be r b e difficulty a d da in and are incapable of serving as internal refrigtransferri as of p y r w S ll 00 rant, in whi h c s it i necessary t provide tained volatile, inflammable material from one some other cooling agent and to remove the heat se 10 another. of reaction by indirect cooling using heat ex- It is the object of this invention to provide the changer surfaces. The advantages of the indiart with a method and app ra us whe b 0w rect cooling method are, firstly, that it is possible tempe u p ly a 0f isoolefins 0r 0f thereby to keep the refrigerant uncontaminated mixtures of i ol fins an dio fi m y b c nwith other materials, thus eliminating the necesducted in a continuous and expeditious manner. sity for repurifying the refrigerant and, secondly, It is also the object of this invention to prothat it permits a greater choice of materials for vide means for elfectively sealing ofi a low temuse as diluent in the reaction and particularly it perature polymerization zone containing highly permits utilization of isobutylene itself as the volatile, inflammable, and in many cases, toxic principal diluent. materials from the atmosphere and yet which 7 Claims. (Cl. 23260) In view of the low temperatures at which the reaction is conducted, i. e., about 4-0 C. to about C., and the highly volatile and inflammable nature of certain of the reactants, it is obvious 3 permits ready withdrawal of polymer with a minimum of occluded or adsorbed volatile, inflammable material.

It is also an object of this invention to produce high molecular weight polymerizates of isoolefins and copolymerizates of isoolefins and diolefins in finely divided form thereby permitting degassing of the polymers in an extremely simple manner.

It is also an object of this invention to produce high molecular isoolefin polymers and isoolefin-diolefin copolymers in a sufficiently divided condition so that the polymers may be thoroughly degassed and the residue of catalyst removed therefrom by a relatively simple operation thereby making it unnecessary to resort to mechanical treatments such as hot milling and/or Banburying to degas the polymers.

It is a further object of this invention to vaporize unreacted volatile material at a relatively uniform rate and to recover and recycle the valuable materials in the reaction liquid accompanying the polymers leaving the reaction zone.

It is a further object of this invention to provide the art with a method and apparatus whereby a water slurry of finely divided high molecular weight polymerizates obtained by the polymerization of an isoolefin or by the copolymerization of a mixture of an isoolefin and a diolefin at low temperatures in the presence of Friedel- Crafts type catalysts may be produced continuously.

These and other objects will appear more clearly from the detailed description and claims which follow.

It has now been found that it is possible to carry out the reaction in such a manner as to keep the solid polymerizate particles in a finely divided condition suspended in the cold reaction mixture so that a slurry of solid polymer in the cold reaction mixture is obtained which can be handled at low temperature in pumps and pipes and which can be dropped into well-agitated warm water or other liquid whereby the volatile materials are effectively removed as vapors, leaving the polymer as a slurry of finely divided particles suspended in water. This process has the advantage not only of substantially freeing the polymer from the remainder of the unreacted reaction mixture thereby permitting the recycling of the volatile materials through a purification system and thence back into the reactor, but it serves further to seal off the reaction zone and the purification and recycling system from the atmosphere and permits the withdrawal of the polymer into the atmosphere relatively free from volatile, inflammable materials. The process when properly conducted also yields the polymer in finely divided form in a water slurry, whereupon it may be separated, washed and dried in very simple equipment.

The accompanying drawings illustrate several forms of apparatus that may be utilized in carrying out the present invention. In the drawings,

Figure I is a vertical elevation, partly in section of a polymerization and polymer recovery equipment in accordance with the present invention.

Figure II is a diagrammatic vertical elevation showing another form of polymerization and polymer recovery equipment.

Figures III, IV and V are vertical elevations, partly in section or several alternative arrangements of preferred forms of flash tanks and slurry handling equipment.

Referring to the drawings, in Figure I, the

polymerization equipment desirably consists of a reactor member l having a jacket 2 therearound for the circulation of a refrigerant, preferably liquid ethylene. The reactor is equipped with a stirrer 3 carried upon a shaft 4 which is driven by any convenient source of power through gears 5 and a shaft 6. The polymerizable olefinic materials are supplied to the reactor through pipe member i. A second pipe member 8 which preferably is equipped with a nebulizing spray head 9 on its lower end is utilized for supplying the catalyst to the reactants in l. A vapor outlet pipe member H is provided leading from the top of the reactor to a suitable purification and recovery system. The discharge pipe comprises a downwardly extending leg I2 which is connected to an upwardly extending leg 15. The discharge pipe also forms a seal due to the simultaneous presence of a liquid level in both of said legs so that no vapor can back up into the reactor. Jackets 14 and 22 are provided around the discharge pipe for the circulation of a refrigerant such as ethylene. In view of the tendency of the polymer to settle in the discharge or seal pipe and in order to prevent plugging, means may be provided as in the form of a screw conveyor 16 in leg l5 for forcing the solid polymer up this inclined pipe. A supporting shaft I3 is provided for conveyor screw it and extends through a packing gland is and is connected to a source of driving power 2!. The end of the screw conveyor 18 extends into the end of a water slurrying chamber 23. The slurrying chamber 23 preferably consists of a metal tank, one end of which is closed in and provided with an exhaust pipe 24 for the removal of volatilized'hydrocarbon material and delivery of the volatilized hydrocarbon material to the separating and purifying system. The closed portion of the slurrying chamber 23 is desirably provided with a relief pipe 25 passing to a water seal member 26 and thence to an exhaust pipe 27. Within the tank member 23 there are provided a pair of roll members 23 and 29 over which passes a flexible belt member 34 equipped with bucket members 32. The roll 23 is positioned well up inside the closed end of the tank member 23 as shown in Figure l, and the roll member 29 is positioned near the bottom and to one side of the closed portion of the tank. A partition 33 is likewise provided and the tank is filled nearly full of water. Another roll member 34 is likewise provided near the top of the uncovered portion of the tank member 23 and a belt member 35, preferably in the form of an endless wire screen is provided passing over the roll member 34 and over the far end of the open portion of the tank 23. The belt 35 is carried on additional rollers 36 and 37 under a water spray member 38, over a collector trough 39 and another guide roller 4| to an end roller 42 under a pressure roller 43.

In the operation of the various embodiments of the invention, the polymerization mixture is prepared in convenient mixing tanks (not shown). The polymerizable material desirably consists of isobutylene alone or of from about '70 to 99.5 wt. percent of an isoolefin having from 4 to 8 carbon atoms per molecule, isobutylene being the preferred material; and from about 30 to 0.5 wt. percent of a diolefin. The diolefin may be butadiene or may be substantially any of the substituted butadienes up to those having from 10 to 12 carbon atoms per molecule. Preferred diolefins are isoprene, piperylene and dimethyl butadiene. Alternatively, the non-conjugated diolefins such as dimethylallene or the triolefins such as myrcene, having up to or 12 carbon atoms per molecule, may also be used. The polymerization mixture contains in addition from 100 parts to 700 or more parts of liquid ethylene, The presence of the liquid ethylene cools the mixture to a temperature between '--97 C. and l03 C,, which temperature is well maintained by the presence of liquid ethylene in the refrigerating jacket 2 of the polymerization reactor i.

The cold polymerization mixture is delivered through the pipeline 1 to the reactor l and the stirrer 3 is put into operation. When the reactor is filled to the overflow level, the polymerization catalyst is delivered through a pipe 8 and the spray head 9.

The catalyst conveniently consists of a solution of a Friedel-Crafts type catalyst such as aluminum chloride, in solution in. a noncomplex-forming, low-freezing solvent such as ethyl or methyl chloride or propyl chloride or other monoor poly-halide containing up to 3 or 4 carbon atoms per molecule or other noncomplex-forming solvent which is liquid at tem-' peratures below about C., e. g. carbon disulphide or sulphuryl chloride. The list of usable Friedel-Crafts catalysts is well shown by N. O. Calloway in his article on Th Friedel-Crafts Synthesis in the issue of Chemical Reviews published for the American Chemical Society at Baltimore in 1935, being volume XVII, number 3, the article beginning on page 3 7, the list being particularly well shown on page 375. The re actants, catalysts, solvents and the like and the general properties of the polymers formed are described in U. S. Patent 2,203,873 and in the Australian Patent 112,875 as mentioned earlier herein. I

This catalyst is preferably supplied to the reaction mixture in the form of a finely divided spray or mist onto the surface of the rapidly stirred reaction mixture but it may be added in afine stream into the turbulent zone adjacent to the stirrer 3 or may be added by any other convenient means which will yield a rapid and thorough dispersion of the catalyst liquid into the olefinic mixture. The reaction proceeds promptly to form a slurry of solid polymer particles in unreacted olefinic components. The rate of catalyst delivery with respect to the rate of delivery of fresh reactants is preferably adjusted to such a relationship that the proportion of solid polymer in the reacted mixture is less than about 20%.- The polymerization reaction being exothermic, heat is liberated as the solid "polymer forms. The temperature of the reaction mixture is maintained at a low level by allowing a portion of the ethylenein the mixture to vaporize. The vaporized ethylene plus smaller amounts of reactant vapors and catalyst solvent vapors escape to the recovery system through line i I.

When the reactor is filled to the overflow level, the addition of further olefinic material through the pipeline '1 and catalyst solution through line 8 causes an overflow of the polymer slurry through the pipe l2 to the screw conveyor IS. The screw conveyor forces the polymer slurry upward through the pipe IE to the closed portion of the tank 23 and delivers the solid polymer with from about 300% of its weight to about 900% of its weight of liquid, unreacted, olefinic material and drops it into the warm water in the tank 23. The warm water volatilizes out most of the volatile components and at the same time deactivates and washes out the deactivated catalyst. Steam is supplied to the flash tank water at 10, to replace the heat lost due to vaporization of the unreacted materials. The polymer tends to float upon the surface of the water and is caught by the buckets 32 on the belt 3| and carried downward through the water under the sealin wall 33 and discharged on the far side of the sealing wall. The volatilized oleflnic material passes through the pipe 24 to the purifying and recycling system for reuse. The solid polymer discharged under the sealing wall contains less than 10%, usually less than 1% of volatile hydrocarbon materials. The solid polymer again floats to the surface and is caught upon the upper surface of the belt 35, carried under the water spray from the spray member 38, through the squeeze roll .3 and is delivered for such further processing as is desired, this further processing desirably including a treatment in an oven dryer in order to dry the polymer and drive off any residual volatile material and also, if desired, a milling treatment to compact it into a coherent sheet for shipment and compounding.

Figure II shows a somewhat different. and in some respects simpler, flashing system and may best be followed by referring back to Figure I. The reactor 10! is of the same type as shown in Figure I, using an internal refrigerant. It IS provided with feed and internal refrigerant inlets !02 and H13, agitator I64, catalyst solution inlet I 05 and cold slurry discharge line N16. The discharge line IE5 is surrounded by a jacket I01, providing a dead air space around 106 as insulation between the cold reaction zone and the rela tively warm flashing zone. The slurry of polymer in cold unreacted hydrocarbon, diluent and/or internal refrigerant mixture enters the flashing zone through a large diameter chimney IE9 and drops into the water in flash tank I08. The water in said flash tank is maintained at a suitably warm temperature to F.) by means of steam distributor I22. The contents of the flash tank are agitated by reciprocating agitator H3 provided with inclined paddles H2 and actuated by eccentric drive shaft H4. Flashed vapors are returned to a recovery system at I26, through discharge pipe H0. The vapor discharge line is provided with a water seal I24 and a mercury seal I25, designed to relieve any sudden surges exceeding one or two pounds per square inch above atmospheric pressure. The Water seal and the mercury seal discharge to the atmosphere, the water seal being set to discharge at a lower pressure than the mercury seal.

The polymer entering the flashing zone is aided in its journey to the flash tank proper by Water spray III, which also keeps polymer from sticking to the walls of the chimney. Steam introduced at I21 prevents formation of ice at or near the entrance of cold reaction mixture to the flashing zone. The polymer suspended in the water in tank I08 by the reciprocating action of paddles H2, passes in succession under baflles H5 and H6 into discharge compartment H1 wherein the polymer floats to the surface and can be removed by hand for drying and milling treatment. Water is kept in circulation by pumping out of compartment ll! through line H8, pump I20, line IZI and back into the flashing zone through spray H l. Fresh water is added in small amounts through line I28 and corresponding amounts of water are purged from the system through drain H9.

Referring to Figure III, the polymerization step is conducted in a tube bundle type of reactor such as described in the patent application of Bannon (U. S. Serial No. 448,575, filed June 26, 1942) now abandoned. In this reactor no internal refrigerant is used, all the heat of reaction being transferred through the reactor walls to an external refrigerant. The liquid refrigerant, suitably ethylene as in Figure I, is introduced into the space between tube sheets 202 and 203 through line 20 5, while vaporized refrigerant leaves the said space through line 205. Precooled reactant mixture of isoolefln and diolefin as described in connection with Figure I, and

in addition containing 0 to about 20 parts of diluent per part of reactant hydrocarbon mixture, enters the reactor through line 206. Suitable diluents are ethyl chloride, methyl chloride, isobutane, and similar materials. Catalyst solution, as described in connection with Figure I, is added through line 201 provided with a suitable dispersing nozzle, 208. The reactant mixture is thoroughly agitated by impeller type agitator 208, so that a circulation of the reacting mixture is produced up through central tube M0 and down through a plurality of peripheral smaller tubes 21!, set between tube sheets 202 and 203. The reactor is maintained essentially full of liquid, a mixture of relatively finely divided polymer and excess unreacted hydrocarbons plus diluent overflowing from the reactor through line H2 in amount corresponding to the material feed to the reactor through lines 206 and 201. The size of line M2 is so chosen,

in relation to the throughput of material through 1 the reactor, that the line is full of liquid and the velocity of flow of slurry into flash tank'2l3 is preferably over about 3 feet per second or high enough to keep the line running full. Flash tank H3 is a relatively large vessel designed to withstand mild pressure surges, of the order of 1-10 lbs/sq. in. having a relatively large vapor space, providing preferably several minutes nominal hold-up of the vapors in the flash tank. The tank is supplied with water maintained at a suitable level by means of level control 2E8 actuating flow control valve 2% which controls the rate of withdrawal of slurry from the flash tank. The water slurry is maintained at a suitably elevated temperature level, for example at 100 to 180 F., by means of steam injected through pipe 2E6; and is kept well agitated by means of turbine type agitator 2'15. For the production of a finely divided uniform slurry it has been found preferable to supply agitation such that at least 2 to 10 hp. is absorbed by each 1,000 gallons of liquid. Splash plate 214 is provided opposite the inlet line 2l2 to provide for immediate break up of the incoming stream of polymer and'low boiling liquids and for dispersing them in a copious stream of water flowing from line 2|? and pump 22'! over the said splash plate. In this way pro vision is made for warming up the polymer and volatilizing the liquids while the polymer is in a finely divided condition, and denying said polymer an opportunity for sticking together during this warming up period when it is particularly tacky. The vapors leave the flashing zone through line 239 and are fed to compression, drying, liquefication, and distillation equipment for recovery and return to the reaction zone. The slurry of polymer in water leaves the flashing zone through line 259 and control valve 240, as mentioned above, and passes into stripping vessel 220 wherein a suitable sub-atmospheric pressure is maintained. The purpose of this stripping zone is to complete as far as possible removal of volatile materials from the polymer and from the water. In this way loss of valuable reactant or diluents is minimized, as are fire and other hazards. In addition to the removal of these volatile materials from the polymer, the stripping operation when combined with properly controlled hot air drying in a thru-circulation, tunnel type dryer, makes it possible to achieve essentially complete degassing without necessitating resort to heavy mechanical treatment. The stripping vessel is, like the flashing vessel, provided with an agitator 238, a steam injector 231, and a vapor outlet 22L In this illustration the pressure in the stripping zone is maintained at about 2 to 5 #/sq. in. abs. by means of a 2-stage steam injector 222, which embodies condensers before and after each ejector stage. The condensate from the low pressure stages is returned to the stripper through leg 223 while the recovered vapors are sent to the flashing zone through line 224. The slurry leaves the stripper through line 225 with the aid of pump 226 at a rate controlled by flow controller 228, and passes into weir box 229 from which it is distributed over vibrating screen 230. Excess water drains through the vibrating screen into tank 231, the moist polymer discharged from the end of vibrating screen at 234 containing a substantial percentage of water. Said moist polymer is supplied to an endless screen passing through a tunnel dryer of the through-circulation type in which hot air is recirculated over steam coils and down through a bed of material on the screen. Fresh air enters at the discharge end of the tunnel and moist air is exhausted to the atmosphere at various points along the dryer. Drying temperatures of up to about 250 F. are utilized and these conditions of good contact of the rapidly moving air stream with finely divided polymer suffice to drive off residual volatile materials which would ordinarily give rise to blister formation during vulcanization if they were not removed. Water draining through vibrating screen 230 into tank 231 is returned to the flash tank 2i3 by means of pump 235 and flow controller 236 in order to save water and any valuable materials contained therein as discussed below.

Tank 23! is provided with fresh water makeup and a Water overflow to provide for purging any undesirable accumulations. It will be noted in Figure III that flow controllers shown in slurry lines utilize a Venturi meter instead of the usual orifice type of meter as the measuring device in order to avoid plugging by the solid polymer particles. The control valves are also of a special streamlined designwhich are not readily plugged by solid material. In order to take care of any large surges in pressure as may occur if a large slug of polymer or of reaction mixture should strike the water in the tank, a suitable safety valve 250 may be provided on the flash chamber.

In Figure IV a modification of the system shown in Figure III is shown which provides in many cases smoother and more easily controllable operation. The line 3l2 delivering cold slurry from the reactor to the flash tank is increased in size to allow passage of larger particles of solids although sacrificing in velocity of flow. This line 3l2 is also tilted upward to provide an effective liquid seal on the reactor. In this case the slurry leaves the reactor through line 3l2 at a velocity of 1 to 3 feet per second and discharges into the flash tank in a downward direction. To prevent-water vapor from the flash tank getting back into the line 312 which may not run full, conical hood 3 is provided over this discharge end of piping 312. This hood is of the type described in U. S. Patent application Serial No. 502,258, filed September 14, 1943 by Messrs. E. V. Murphree, W. W. Waterman and A. D. Green, now Patent No. 2,395,901, and is for the purpose of preventing access of water vapor to the immediate neighborhood of a cold reactor discharge pipe, thus preventing build-up of volves the preparation of solid polymers which have a considerable range of molecular weight ice or icy hydrates in this region. The hood is supplied with a dry flushing gas through line 340. The flushing gas may be an inert gas such as CO2, nitrogen, methane, or more conveniently, a small stream of dry recycle gas from the recovery system. A velocity of flushing gas at the bottom of the conical hood of 10 to per minute has been found suflicient to prevent icing.

The polymer and cold liquid falling from the hood is caught by a ragidly moving sheet of water from line 3!! discharging through jet 3 12 and directed at the center of the surface of the water in the flash tank. For this purpose a 1 x '7" rectangular nozzle may be advantageously used for a water flow of around 400 gallons per minute. To protect the tank from sharp thermal shock in case of failure of the water jet a skirt or baflle 343 is provided, a small amount of steam being admitted behind it through line 34 3. In this modification two turbine type agitators 3|5 are used to provide a somewhat better distribution of agitation of the slurry in the tank, and the slurry is withdrawn from the middle of the tank at 3l9 instead of at the bottom to give a more uniform solids concentration in the exit slurry.

The level control system of Figure IV has been modified so that a constant level is held in the stripping zone as well as in the flashing zone. In this case the stripper level actuates control of the rate of flow of slurry from the flashing zone to the stripping zone by control valve 32d and the liquid level in the flashing zone controls the return of water to said flashing zone from the vibrating screen sump by means of control valve 3H8. In this way a minor upset in flow in any part of the system is less likely to cause improper levels to be held in either of the two zones. It is important to maintain the proper level, since too low a level results in an inordinately heavy and difiicultly handled slurry while too high a level increases the volume of liquid being agitated I and hence decreases agitation per unit volume to the extent that considerable settling of the polymer to the surface tends to occur.

Figure V is a further modification of the system described in detail in Figure III. In this case the flow controls are as in Figure IV and the only further modification from the scheme of Figure III beyond those mentioned above corresponding to Figure IV is the omission of the hood and flushing gas at the inlet flash tank, reliance being placed upon eificient action of an oblique water curtain from line Ml entering the tank through jet 442 above the reactor discharge pipe, and upon a high velocity in the reactor discharge line M2 to prevent icing at the entrance to the flash tank.

In the first two embodiments of the invention the slurry is not as finely divided as is produced in the equipment shown in Figures III, IV and V.

. It may be seen that the present invention inand resulting physical characteristics depending upon the operating conditions chosen and maintained in the reaction zone. In general, when the polymerization is conducted in the presence of a non-solvent diluent at suitably low temperatures, the polymer is relatively non-sticky in the reaction zone. When removed from the reaction zone and warmed in the presence of adhering reaction liquids, it becomes exceedingly sticky, even in the case of the higher moleclular weight isoolefin-diolefin copolymer type products. After evaporation of the volatiles is completed, the stickiness of the product depends to a large extent on the molecular weight distribution in the polymer.

In order to avoid the agglomeration of polymer particles due to this tackiness, this invention provides for immediately dispersing the material leaving the reaction zone within a large body of warm fluid which may be either a non-solvent for the polymer, such as water, alcohols, ketones, aqueous solutions or the like or a solvent for the polymer, such as light naphtha, benzene, etc. This large body of fluid is supplied with heat at a rate adequate to maintain it at a sufficiently elevated temperature to insure rapid heat transfer to the coldliquid and prevent solid (ice or wax) formation. The body of fluid is also vigorously agitated to insure efficient heat transfer and/or the prevention of occlusion of volatile liquids or pockets surrounded by polymer, ice or other solid matter which would explode when heated sufliciently to volatilize the occluded liquid. The vapor space in the flashing zone is made sufficiently large to substantially even out the flow of gas therefrom to the recovery equipment and the gas outlet to the recovery and recycle system is adequately protected against surges. The pressure under which the flash tank is operated may be maintained close to atmos pheric pressure or it may be sufficiently high so that while the reaction liquids are rapidly vaporized at the relatively warm temperature of the flashing zone, the vapors may readily be condensed with the aid of cooling water without the air of gas compressors or refrigeration. At at mospheric or subatmospheric pressure is maintained in the second flashing zone, the vapors therefrom being vented or compressed and combinedwith those from the first stage. This type of operation is somewhat easier with reaction diluents less volatile than methyl chloride. The polymer is removed from the flashing zone through a seal of the said. flashing liquid thereby preventing loss or escape of the vapors liberated in the flashing zone.

The second flashing or stripping zone may or may not be included. When it is provided, it is operated at a pressure substantially lower than that of the first flashing zone and with or without additional supply of heat or stripping vapors.

Various auxiliary chemicals may be added to the flash tank liquid. Zinc stearate mentioned above or other divalent metal salts of higher fatty acids in general or materials such as clays, pigments or carbon black may be added to the liquid in the flash tank in order to aid the maintenance of the polymer as discrete particles in the slurry. Other agents such as stabilizers like phenyl-betanaphthylamine, diphenylamine, sulfur or other materials which are useful in the finished polymer may be added to the flashing liquid as a matter of convenience. It is also desirable to add agents which prevent the build-up of acidity in the flash tank liquid because of the fact that the catalysts used normally liberate acid upon hydrolysis, which while small in. amount eventually builds up to an objectionable degree unless a considerable purging of the liquid is allowed to take place. Suitable agents for this purpose include soda ash, caustic soda, calcium oxide, masnesium oxide or other alkaline materials.

The foregoing description is illustrative of the present invention. It will be obvious to those skilled in this art, however, that numerous variations are possible without departing from the purview of this invention as defined by the following claims.

What is claimed is:

1. A low temperature polymerization plant which comprises in combination a closed reaction tank, a refrigeration jacket substantially surrounding the reaction tank, an externally driven mechanical agitator within the lower portion of the reaction tank, a plurality of feed lines leading to the lower portion of the reaction tank, an exhaust line connected to the overhead portion of the reaction tank, an overflow line interconnecting an intermediate portion of said reaction tank with the upper portion of an adjacent closed flash tank, said overflow line extending upwardly from the reaction tank so as to constitute a liquid seal between the two tanks and having its discharge end directed downwardly within the flash tank, a steam inlet line leading into the lower portion of the flash tank, a vapor exhaust line leading from the overhead portion of the flash tank, an outlet conduit leading from the lower portion of the flash tank to an adjacent closed vacuum drum, an automatic flow control valve in said outlet conduit arranged to maintain a predetermined liquid level in the vacuum drum, a recycle conduit inter-connecting the lower portion of the flash tank with a spray de vice positioned within the upper portion of the flash tank in 'close proximity to the discharge end of the overflow line and arranged to discharge a hot liquid spray into the stream issuing from the overflow line, a pump connected in the recycle conduit, an externally driven agitator in the liquid space portion of the flash tank, a gas exhaust pipe leading from the overhead portion of the vacuum drum to the vapor space portion of the flash drum, a steam ejector connected to said gas exhaust pipe and arranged to reduce the pressure in the vacuum drum, an agitation device in the lower portion of the vacuumdrum, a discharge conduit leading from the bottom portion of the vacuum drum to a recovery system wherein polymer particles are separated from water, a return line adapted to recycle the separated water from the recovery system to the flash tank, and a flow control valve in the last named return line adapted to maintain the liquid level in the flash tank below the discharge end of the said overflow line.

2. A polymerization plant according to claim 1 wherein the discharge end of the overflow line in the flash tank is located within a hood connected to a source of dry gas.

3. A polymerization plant according to claim 1 wherein an inclined splash plate is provided in the flash tank opposite the respective discharge ends of the overflow line and of the recycle conduit.

4. Apolymerization plant according to claim 1 wherein the overflow line is provided with an external cooling jacket.

5. A polymerization plant according to claim 1 wherein each of the said flow control valves comprises a Venturi meter.

6. A polymerization plantaccording to claim 1 wherein the spraying device of the recycle conduit is a wide nozzle located in the flash tank closely below the discharge end of the overflow line and arranged to pass a water curtain across the path of the stream discharged from the overflow line.

7. A polymerization plant according to claim 2 wherein a heated baiile is provided above the liquid level next to the flash tank wall so as to protect the wall from thermal shock.

ARTHUR DONALD GREEN.

REFERENCES CITED The following references are of record in the flle of this patent:

UNITED STATES PATENTS Number Name Date 2,240,618 Harris May 6, 1941 2,378,138 Gaylor June 12, 1945 2,384,298 Green Sept. 4, 1945 2,391,393 Cofiman Dec. 25, 1945 2,436,767 Gerlicher Feb. 24, 1948 

1. A LOW TEMPERATURE POLYMERIZATIOPN PLANT WHICH COMPRISES IN COMBINATION A CLOSED REACTION TANK, A REFRIGERATION JACKET SUBSTANTIALLY SURROUNDING THE REACTION TANK, AND ECTERNALLY DRIVEN MECHANICAL AGITATOR WITHIN THE LOWER PORTION OF THE REACTION TANK, A PLURALITY OF FEED LINES LEADING TO THE LOWER PORTION OF THE REACTION TANK, AN EXHAUST LINE CONNECTED TO THE OVERHEAD PORTION OF THE REACTION TANK, AN OVERFLOW LINE INTERCONNECTING AN INTERMEDIATE PORTION OF SAID REACTION TANK WITH THE UPPER PORTION OF AN ADJACENT CLOSED FLASH TANK, SAID OVERFLOW LINE EXTENDING UPWARDLY FROM THE REACTION TANK SO AS TO CONSTITUTE A LIQUID SEAL BETWEEN THE TWO TANKS AND HAVING ITS DISCHARGE END DIRECTED DOWNWARDLY WITHIN THE FLASH TANK, A STEAM INLET LINE LEADING INTO THE LOWER PORTION OF THE FLASH TANK, A VAPOR EXHAUST LINE LEADING FROM THE OVERHEAD PORTION OF THE FLASH TANK, AN OUTLET CONDUIT LEADING FROM THE LOWER PORTION OF THE FLASH TANK TO AN ADJACENT CLOSED VACUUM DRUM, AN AUTOMATIC FLOW CONTROL VALVE IN SAID OUTLET CONDUIT ARRANGED TO MAINTAIN A PREDETERMINED LIQUID LEVEL IN THE VACUUM DRUM, A RECYCLE CONDUIT INTER-CONNECTING THE LOWER PORTION OF THE FLASH TANK WITH A SPRAY DEVICE POSITIONED WITHIN THE UPPER PORTION OF THE FLASH TANK IN CLOSE PROXIMITY TO THE DISCHARGE END OF THE OVERFLOW LINE, A PUMP CONNECTED IN THE CHARGE A HOT LIQUID SPRAY INTO THE STREAM ISSUING FROM THE OVERFLOW LINE, A PUMP CONNECTED IN THE RECYCLE CONDUIT, AN EXTERNALLY DRIVEN AGITATOR IN THE LIQUID SPACE PORTION OF THE FLASH TANK, A GAS EXHAUST PIPE LEADING FROM THE OVERHEAD PORTION OF THE VACUUM DRUM TO THE VAPOR SPACE PORTION OF TH FLASH DRUM, A STEAM EJECTOR CONNECTED TO SAID GAS EXHAUST PIPE AND ARRANGED TO REDUCE THE PRESSURE IN THE VACUUM DRUM AN AGITATION DEVICE IN THE LOWER PORTION OF THE VACUUM DRUM, A DISCHARGE CONDUIT LEADING FROM THE BOTTOM PORTION OF THE VACUUM DRUM TO RECOVERY SYSTEM WHEREIN POLYMER PARTICLES ARE SEPARATED FROM WATER, A RETURN LINE ADAPTED TO RECYCLE THE SEPARATED WATER FROM THE RECOVERY SYSTEM TO THE FLASH TANK, AND A FLOW CONTROL VALVE IN THE LAST NAMED RETURN LINE ADAPTED TO MAINTAIN THE LIQUID LEVEL IN THE FLASH TANK BELOW THE DISCHARGE END OF THE SAID OVERFLOW LINE. 